CN115677615B - Fluorescent chiral liquid crystal film and preparation method thereof - Google Patents
Fluorescent chiral liquid crystal film and preparation method thereof Download PDFInfo
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- CN115677615B CN115677615B CN202211128378.0A CN202211128378A CN115677615B CN 115677615 B CN115677615 B CN 115677615B CN 202211128378 A CN202211128378 A CN 202211128378A CN 115677615 B CN115677615 B CN 115677615B
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002019 doping agent Substances 0.000 claims abstract description 36
- 239000007850 fluorescent dye Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- -1 cyano, methyl Chemical group 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 55
- 239000010453 quartz Substances 0.000 claims description 52
- 239000000463 material Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 21
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- 239000000203 mixture Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 8
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- 239000007810 chemical reaction solvent Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
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- VUQVJIUBUPPCDB-UHFFFAOYSA-N (1-bromo-2,2-diphenylethenyl)benzene Chemical group C=1C=CC=CC=1C(Br)=C(C=1C=CC=CC=1)C1=CC=CC=C1 VUQVJIUBUPPCDB-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 4
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- 238000005859 coupling reaction Methods 0.000 claims description 4
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- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
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- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
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- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 claims description 2
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 claims description 2
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 claims description 2
- 235000012000 cholesterol Nutrition 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229960002479 isosorbide Drugs 0.000 claims description 2
- 229940041616 menthol Drugs 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
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- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 claims description 2
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- 239000004814 polyurethane Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 1
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- 238000004519 manufacturing process Methods 0.000 claims 1
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 57
- 239000010408 film Substances 0.000 description 41
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 32
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- 238000004090 dissolution Methods 0.000 description 12
- 239000011521 glass Substances 0.000 description 10
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- 238000005406 washing Methods 0.000 description 9
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000002604 ultrasonography Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
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- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000002990 phenothiazines Chemical class 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 2
- 239000005264 High molar mass liquid crystal Substances 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- OIPZAGXNNDLAEW-UHFFFAOYSA-N 3,7-dibromo-10-(4-methoxyphenyl)phenothiazine Chemical compound C1=CC(OC)=CC=C1N1C2=CC=C(Br)C=C2SC2=CC(Br)=CC=C21 OIPZAGXNNDLAEW-UHFFFAOYSA-N 0.000 description 1
- FULBEMKAJCHNHO-UHFFFAOYSA-N 3,7-dibromo-10-(4-methylphenyl)phenothiazine Chemical compound BrC=1C=CC=2N(C3=CC=C(C=C3SC=2C=1)Br)C1=CC=C(C=C1)C FULBEMKAJCHNHO-UHFFFAOYSA-N 0.000 description 1
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- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical group [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 1
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Landscapes
- Liquid Crystal Substances (AREA)
Abstract
The invention provides a fluorescent chiral liquid crystal film and a preparation method thereof. The preparation method of the fluorescent liquid crystal film comprises the following steps: dissolving and mixing liquid crystal molecules, fluorescent compounds, chiral dopants and photoinitiators, and obtaining the fluorescent liquid crystal film through photopolymerization reaction; the fluorescent compound has the following molecular formula:wherein R is selected from cyano, methyl, ethyl, propyl, methoxy or carboxyl. The chiral dopant molecule can induce the liquid crystal molecules to assemble to form a chiral nematic supermolecule spiral structure. The preparation method of the fluorescent liquid crystal film is simple, the operation is convenient, the raw material consumption is low, and the prepared fluorescent chiral liquid crystal film has stable performance.
Description
Technical Field
The invention belongs to the field of circularly polarized luminescent materials, and particularly relates to a fluorescent chiral liquid crystal film and a preparation method thereof.
Background
The Circularly Polarized Luminescence (CPL) reflects the difference of the left and right circularly polarized light emitted by the chiral luminescent material in the excited state. Circularly polarized light emitting material for three-dimensional display and circularly polarizationThe LED and information encryption fields have wide application prospects. Luminous asymmetry factor (g) lum ) Is a key parameter for evaluating the performance of the circularly polarized luminescent material, g lum ＝2(I L -I R )/(I L +I R ) Wherein I L And I R The intensities of left circularly polarized light and right circularly polarized light, respectively. Larger g lum Is important for realizing various practical applications of CPL active materials. Therefore, how to further increase the g of CPL material lum Is very urgent and challenging. So far, strategies such as chiral supermolecule assembly, luminescence up-conversion, resonance energy transfer, chiral luminescence liquid crystal and the like have appeared, and the g of CPL material can be obviously improved lum 。
CPL active materials based on chiral liquid crystal systems have received great attention not only because of their unique optical properties, which can give higher g lum CPL active material of value and also because of its good versatility to many luminescent substances. Thus, chiral luminescent liquid crystal materials are considered to be prepared with high g lum Is an ideal choice of CPL active material. However, most of the circularly polarized light-emitting liquid crystal materials reported at present are small molecule liquid crystals, and are usually required to be placed in a liquid crystal box for use, and practical application is not utilized. Therefore, there is a need to develop a circularly polarized light-emitting polymer liquid crystal thin film material which can exist stably.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a fluorescent chiral liquid crystal film. The material is a circular polarization luminescent material of chiral nematic liquid crystal containing fluorescent molecules. Fluorescent molecules are added into a chiral liquid crystal system with structural color, photocrosslinking solidification is carried out through ultraviolet lamp irradiation, and a series of chiral high molecular liquid crystal films with stable polymer networks are prepared, and the films can emit circularly polarized light and have higher luminous asymmetry factor g lum Values.
A first object of the present invention is to provide a fluorescent compound having the following molecular formula:
wherein R is selected from cyano, methyl, ethyl, propyl, methoxy or carboxyl.
A second object of the present invention is to provide a method for preparing the fluorescent compound, comprising the steps of:
(1) Will beAdding a reaction solvent into the bisboronic acid pinacol ester, a catalyst and an alkaline agent to perform heating reaction, and performing solid-liquid separation on the reaction liquid to obtain a solid substance; wherein R is selected from cyano, methyl, ethyl, propyl, methoxy or carboxyl:
(2) Mixing the solid substance obtained in the step (1) with triphenylbromoethylene, an alkaline agent and a coupling catalyst in a reaction solvent, and performing a heating reaction to obtain the fluorescent compound;
in one embodiment of the present invention, in step (1), the heating reaction conditions: reacting for 12-24 hours at 100-110 ℃.
In one embodiment of the present invention, in step (1), the reaction solvent is selected from 1, 4-dioxane.
In one embodiment of the invention, in step (1), the catalyst is selected from [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride and/or bis (triphenylphosphine) palladium dichloride.
In one embodiment of the present invention, in step (2), the heating reaction conditions: reacting for 12-24 hours at 110-120 ℃.
In one embodiment of the invention, in step (2), the coupling catalyst is selected from (Ph 3 P)PdCl 2 And/or tetrakis (triphenylphosphine) palladium.
The third object of the invention is to provide the application of the fluorescent compound in preparing fluorescent chiral liquid crystal film.
The fourth object of the present invention is to provide a fluorescent chiral liquid crystal film prepared from the fluorescent compound.
The fifth object of the present invention is to provide a preparation method of the fluorescent chiral liquid crystal film, comprising the following steps:
(1) Mixing and dissolving liquid crystal molecules, chiral dopants, fluorescent compounds and photoinitiators in a solvent to obtain a liquid crystal mixture;
(2) Uniformly coating the liquid crystal mixture obtained in the step (1) between two substrates to form a sandwich structure, heating to remove the solvent, performing photopolymerization under ultraviolet irradiation, and removing the substrates to obtain a cured film, namely the fluorescent chiral liquid crystal film.
In one embodiment of the present invention, in step (1), the solvent is selected from one or more of dichloromethane, ethyl acetate, tetrahydrofuran, chloroform and acetone.
In one embodiment of the invention, in step (1), the liquid crystal molecules are selected from one or more of the following compounds:
in one embodiment of the present invention, preferably, the liquid crystal molecules are selected from one or more of the following compounds:
in one embodiment of the present invention, in step (1), the chiral dopant is selected fromWherein n is any integer from 0 to 12, and M represents a chiral primitive; the chiral moiety is selected from isosorbide, binaphthyl, cholesterol, menthol or 2- (4, n-propyl) cyclohexyl; r is R 1 Selected from hydrogen, methyl, ethyl, acetyl.
In one embodiment of the invention, the chiral dopant is preferably
In one embodiment of the invention, in step (1), the photoinitiator is selected from one or more of the following compounds:
in one embodiment of the present invention, in the step (1), the mass ratio of the liquid crystal molecules, the chiral dopant, the fluorescent compound and the photoinitiator is 170 to 180:8-13:2-4:8-12.
In one embodiment of the present invention, in step (2), the substrate is selected from quartz plate and/or polyester film; wherein the polyester film monomer material is selected from one or more of polyethylene terephthalate, polyurethane, polymethyl methacrylate and polytrimethylene terephthalate.
In one embodiment of the invention, in step (2), the heating temperature is 55-65 ℃.
In one embodiment of the present invention, in step (2), the ultraviolet light source wavelength range is 365nm.
In one embodiment of the present invention, in step (2), the film thickness is 3 to 11 micrometers.
In one embodiment of the present invention, in the step (2), the ultraviolet irradiation time is 8-15s.
In one embodiment of the present invention, in step (2), the solvent further includes a bubble removal process after evaporation.
Preparation of the fluorescent liquid Crystal film of the inventionA method comprising the steps of: and dissolving and mixing liquid crystal molecules, fluorescent molecules, chiral dopants and photoinitiators, and obtaining the fluorescent liquid crystal film through photopolymerization. The fluorescent molecule is a phenothiazine derivative with aggregation-induced emission (AIE) effect, which has no fluorescence in DMF solution, when different volumes of poor solvent H are added 2 At O, fluorescence was enhanced, showing pronounced AIE properties (shown in FIG. 1). A series of chiral liquid crystal polymer films (shown in figure 2) with structural colors, which have CPL performance (shown in figure 3), are obtained by adding liquid crystal molecular monomers and controlling the proportion of chiral dopants.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The invention adopts the phenothiazine derivative with AIE effect, the derivative can emit light in a solid state, and the fluorescent molecule has high quantum efficiency; liquid crystal materials with various structural colors are prepared by controlling the mass percentages of different chiral dopants, and the obtained materials have high luminous asymmetry factor values.
(2) The chiral dopant molecule can induce the liquid crystal molecules to assemble to form a chiral nematic supermolecule spiral structure.
(3) The preparation method of the fluorescent liquid crystal film is simple, the operation is convenient, the raw material consumption is low, and the prepared fluorescent chiral liquid crystal film has stable performance.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings, in which
FIG. 1 is a graph showing AIE test of fluorescent molecules in test example 1 according to the present invention.
FIG. 2 is a graph of fluorescent liquid crystal films containing different mass percentages of chiral dopants in test example 1 of the present invention.
FIG. 3 is a CPL spectrum of the fluorescent liquid crystal film of test example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
The invention provides a preparation method of a fluorescent chiral liquid crystal film. The material is a circular polarization luminescent material of chiral nematic liquid crystal containing fluorescent molecules. Fluorescent molecules are added into a chiral liquid crystal system with structural color, photocrosslinking solidification is carried out through ultraviolet lamp irradiation, and a series of chiral high molecular liquid crystal films with stable polymer networks are prepared, and the films can emit circularly polarized light and have higher luminous asymmetry factor g lum Values.
A first object of the present invention is to provide a fluorescent compound having the following molecular formula:
wherein R is selected from cyano, methyl, ethyl, propyl, methoxy or carboxyl.
A second object of the present invention is to provide a method for preparing the fluorescent compound, comprising the steps of:
(1) Will beAdding a reaction solvent into the bisboronic acid pinacol ester, a catalyst and an alkaline agent to perform heating reaction, and performing solid-liquid separation on the reaction liquid to obtain a solid substance; wherein R is selected from cyano, methyl, ethyl, propyl, methoxy or carboxyl:
(2) Heating the solid substance obtained in the step (1), triphenylbromoethylene, an alkaline agent and a coupling catalyst in a reaction solvent to react to obtain the fluorescent compound;
the third object of the invention is to provide the application of the fluorescent compound in preparing fluorescent chiral liquid crystal film.
The fourth object of the present invention is to provide a fluorescent liquid crystal film prepared from the fluorescent compound.
A fifth object of the present invention is to provide a method for preparing the fluorescent liquid crystal film, comprising the steps of:
(1) Mixing and dissolving liquid crystal molecules, chiral dopants, fluorescent compounds and photoinitiators in a solvent to obtain a liquid crystal mixture;
(2) Uniformly coating the liquid crystal mixture obtained in the step (1) between two substrates to form a sandwich structure, heating to remove the solvent, performing photopolymerization under ultraviolet irradiation, and removing the substrates to obtain a cured film, namely the fluorescent liquid crystal film.
The reagents used in the invention are all commercially available.
Example 1
The embodiment of the invention provides a method for preparing a fluorescent liquid crystal material 1, which comprises the following steps:
liquid crystal molecule 1
Chiral dopant 1
Fluorescent molecule 1
Photoinitiator 1
(1) Synthesis of fluorescent molecule 1
4- (3, 7-dibromo-10H-phenothiazine-10-) benzonitrile (3.0 g,6.5 mmol), pinacol biborate (4.95 g,19.5 mmol), bis (triphenylphosphine) palladium dichloride (0.3 g,0.43 mmol), potassium acetate (1.9 g,19.5 mmol) and 1, 4-dioxane (120 mL) were added and reacted at 100℃for 15 hours. After the reaction is finished, cooling to room temperature, adding diatomite, filtering to obtain a filtrate, adding an aqueous solution for washing, extracting with dichloromethane, adding anhydrous sodium sulfate into an organic layer for removing water, carrying out suction filtration and rotary evaporation to obtain a yellow solid, adding ethyl acetate for washing, and carrying out suction filtration to obtain a light yellow solid. The resulting pale yellow solid (2.0 g,3.6 mmol), triphenylbromoethylene (3.6 g,10.8 mmol), potassium carbonate (2.5 g,18 mmol), tetrakis (triphenylphosphine) palladium (0.25 g,0.2 mmol) were added to a 100mL three-necked flask, nitrogen was purged, and 45mL toluene and 30mL water were added. And heating and refluxing at 110 ℃ for 15 hours. After the reaction is finished, cooling to room temperature, adding an aqueous solution for washing, extracting with dichloromethane, adding anhydrous sodium sulfate into an organic layer for water removal, filtering and spin-evaporating to obtain oily liquid, adding a small amount of dichloromethane for dissolution, and performing column chromatography separation to obtain the target product fluorescent molecule 1. The yield of the reaction product was 70%.
The fluorescent molecule 1 base is characterized as follows:
1 H NMR(300MHz,DMSO-d 6 ,TMS)δ H :6.74(d,J＝8.1Hz,2H)，6.77-6.88(m,4H)，6.90-7.43(m,32H)，7.79(d,J＝8.5Hz,2H)ppm.
(2) Preparation of fluorescent liquid Crystal Material 1
Liquid crystal molecule 1 (173.02-177.14 mg), chiral dopant 1 (8.86-12.98 mg) and fluorescent molecule 1 (2 mg) are weighed, photoinitiator 1 (12 mg) is dissolved in a glass bottle, dichloromethane is added to dissolve, ultrasonic wave and ultrasound are added to ensure uniform mixing, then liquid crystal mixture is sucked on a quartz plate, the quartz plate is heated at 60 ℃ to volatilize solvent, another quartz plate is covered, and tweezers are used to move the quartz plate to discharge bubbles and make the color of the quartz plate uniform. And irradiating with 365nm ultraviolet lamp for 10 s to perform photopolymerization to obtain cured film.
Example two
The embodiment of the invention provides a method for preparing a fluorescent liquid crystal material 2, which comprises the following steps:
liquid crystal molecule 1
Chiral dopant 2
Fluorescent molecule 1
Photoinitiator 1
The preparation method comprises the following specific steps of:
liquid crystal molecule 1 (177.14 mg), chiral dopant 1 (8.86 mg) and fluorescent molecule 1 (2 mg) are weighed, photoinitiator 1 (12 mg) is put in a glass bottle, dichloromethane is added for dissolution, ultrasonic wave ultrasound is added to ensure uniform mixing, then liquid crystal mixture is sucked on a quartz plate, the quartz plate is heated at 60 ℃ to volatilize solvent, another quartz plate is covered, and tweezers are used for moving the quartz plate to discharge bubbles and make the color of the quartz plate uniform. And irradiating with 365nm ultraviolet lamp for 10 s to perform photopolymerization to obtain cured film.
Example III
The embodiment of the invention provides a method for preparing a fluorescent liquid crystal material 3, which comprises the following steps:
liquid crystal molecule 2
Chiral dopant 1
Fluorescent molecule 1
Photoinitiator 1
The specific steps of the fluorescent preparation of the optical liquid crystal material 3 are as follows:
liquid crystal molecule 1 (177.14 mg), chiral dopant 1 (8.86 mg) and fluorescent molecule 1 (2 mg) are weighed, photoinitiator 1 (12 mg) is put in a glass bottle, dichloromethane is added for dissolution, ultrasonic wave ultrasound is added to ensure uniform mixing, then liquid crystal mixture is sucked on a quartz plate, the quartz plate is heated at 60 ℃ to volatilize solvent, another quartz plate is covered, and tweezers are used for moving the quartz plate to discharge bubbles and make the color of the quartz plate uniform. And irradiating with 365nm ultraviolet lamp for 10 s to perform photopolymerization to obtain cured film.
Example IV
The embodiment of the invention provides a method for preparing a fluorescent liquid crystal material 4, which comprises the following steps:
liquid crystal molecule 1
Chiral dopant 1
Fluorescent molecule 1
Photoinitiator 2
The preparation of the fluorescent liquid crystal material 4 comprises the following specific steps:
liquid crystal molecule 1 (177.14 mg), chiral dopant 1 (8.86 mg) and fluorescent molecule 1 (2 mg) are weighed, photoinitiator 1 (12 mg) is put in a glass bottle, dichloromethane is added for dissolution, ultrasonic wave ultrasound is added to ensure uniform mixing, then liquid crystal mixture is sucked on a quartz plate, the quartz plate is heated at 60 ℃ to volatilize solvent, another quartz plate is covered, and tweezers are used for moving the quartz plate to discharge bubbles and make the color of the quartz plate uniform. And irradiating with 365nm ultraviolet lamp for 10 s to perform photopolymerization to obtain cured film.
Example five
The embodiment of the invention provides a method for preparing a fluorescent liquid crystal material 5, which comprises the following steps:
liquid crystal molecules 3
Chiral dopant 1
Fluorescent molecule 1
Photoinitiator 1
The preparation of the fluorescent liquid crystal material 5 comprises the following specific steps:
liquid crystal molecule 1 (177.14 mg), chiral dopant 1 (8.86 mg) and fluorescent molecule 1 (2 mg) are weighed, photoinitiator 1 (12 mg) is put in a glass bottle, dichloromethane is added for dissolution, ultrasonic wave ultrasound is added to ensure uniform mixing, then liquid crystal mixture is sucked on a quartz plate, the quartz plate is heated at 60 ℃ to volatilize solvent, another quartz plate is covered, and tweezers are used for moving the quartz plate to discharge bubbles and make the color of the quartz plate uniform. And irradiating with 365nm ultraviolet lamp for 10 s to perform photopolymerization to obtain cured film.
Example six
The embodiment of the invention provides a method for preparing a fluorescent liquid crystal material 6, which comprises the following steps:
liquid crystal molecules 3
Chiral dopant 1
Fluorescent molecule 1
Photoinitiator 3
The specific steps for preparing the fluorescent liquid crystal material 6 are as follows:
liquid crystal molecule 1 (177.14 mg), chiral dopant 1 (8.86 mg) and fluorescent molecule 1 (2 mg) are weighed, photoinitiator 1 (12 mg) is put in a glass bottle, dichloromethane is added for dissolution, ultrasonic wave ultrasound is added to ensure uniform mixing, then liquid crystal mixture is sucked on a quartz plate, the quartz plate is heated at 60 ℃ to volatilize solvent, another quartz plate is covered, and tweezers are used for moving the quartz plate to discharge bubbles and make the color of the quartz plate uniform. And irradiating with 365nm ultraviolet lamp for 10 s to perform photopolymerization to obtain cured film.
Example seven
The embodiment of the invention provides a method for preparing a fluorescent liquid crystal material 7, which comprises the following steps:
liquid crystal molecule 1
Chiral dopant 1
Fluorescent molecule 1
Photoinitiator 3
The specific steps for preparing the fluorescent liquid crystal material 7 are as follows:
liquid crystal molecule 1 (177.14 mg), chiral dopant 1 (8.86 mg) and fluorescent molecule 1 (2 mg) are weighed, photoinitiator 1 (12 mg) is put in a glass bottle, dichloromethane is added for dissolution, ultrasonic wave ultrasound is added to ensure uniform mixing, then liquid crystal mixture is sucked on a quartz plate, the quartz plate is heated at 60 ℃ to volatilize solvent, another quartz plate is covered, and tweezers are used for moving the quartz plate to discharge bubbles and make the color of the quartz plate uniform. And irradiating with 365nm ultraviolet lamp for 10 s to perform photopolymerization to obtain cured film.
Example eight
The embodiment of the invention provides a method for preparing a fluorescent liquid crystal material 8, which comprises the following steps:
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liquid crystal molecules 4
Chiral dopant 2
Fluorescent molecule 1
Photoinitiator 4
The preparation of the fluorescent liquid crystal material 8 comprises the following specific steps:
liquid crystal molecule 1 (180.14 mg), chiral dopant 2 (10 mg) and fluorescent molecule 1 (3 mg) are weighed, photoinitiator 4 (8 mg) is put in a glass bottle, acetone is added for dissolution, ultrasonic wave is adopted to ensure uniform mixing, then liquid crystal mixture is sucked on a quartz plate, the quartz plate is heated at 60 ℃ to volatilize solvent, another quartz plate is covered, and tweezers are used to move the quartz plate to discharge bubbles and make the color of the quartz plate uniform. And irradiating with 365nm ultraviolet lamp for 10 s to perform photopolymerization to obtain cured film.
Example nine
The embodiment of the invention provides a method for preparing a fluorescent liquid crystal material 9, which comprises the following steps:
liquid crystal molecules 5
Chiral dopant 2
Fluorescent molecule 2
Photoinitiator 3
The specific steps for preparing the fluorescent liquid crystal material 9 are as follows:
(1) The preparation method of fluorescent molecule 2 comprises the following steps:
into a 250mL round bottom flask was charged 3, 7-dibromo-10- (p-tolyl) -10H-phenothiazine (2.30 g,5 mmol), pinacol biborate (3.80 g,15 mmol), bis (triphenylphosphine) palladium dichloride (0.23 g,0.33 mmol), potassium acetate (1.46 g,15 mmol), and 1, 4-dioxane (90 mL) was added and reacted at 100℃for 15 hours. After the reaction is finished, cooling to room temperature, adding diatomite, filtering to obtain a filtrate, adding an aqueous solution for washing, extracting with dichloromethane, adding anhydrous sodium sulfate into an organic layer for removing water, carrying out suction filtration and rotary evaporation to obtain a yellow solid, adding ethyl acetate for washing, and carrying out suction filtration to obtain a light yellow solid. The resulting pale yellow solid (1.9 g,3.6 mmol), triphenylbromoethylene (3.6 g,10.8 mmol), potassium carbonate (2.5 g,18 mmol), tetrakis (triphenylphosphine) palladium (0.25 g,0.2 mmol) were added to a 100mL three-necked flask, nitrogen was purged, and 45mL toluene and 30mL water were added. And heating and refluxing at 110 ℃ for 15 hours. After the reaction is finished, cooling to room temperature, adding an aqueous solution for washing, extracting with dichloromethane, adding anhydrous sodium sulfate into an organic layer for water removal, carrying out suction filtration and rotary evaporation to obtain oily liquid, adding a small amount of dichloromethane for dissolution, and carrying out column chromatography separation to obtain a target product fluorescent molecule 2. The yield of the reaction product was 65%.
The fluorescent molecule 2 base is characterized as follows:
1 H NMR(300MHz,DMSO-d 6 ,TMS)δ H :3.82(s,3H),6.85(d,J＝8.1Hz,2H)，6.70-6.83(m,4H)，6.95-7.25(m,32H)，7.50(d,J＝8.5Hz,2H)ppm.
(2) Liquid crystal molecules 5 (177.14 mg), chiral dopants 1 (12.89 mg) and fluorescent molecules 2 (2 mg) are weighed, a photoinitiator 1 (12 mg) is put in a glass bottle, dichloromethane is added for dissolution, ultrasonic waves are added for ensuring uniform mixing, then a liquid crystal mixture is sucked on a quartz plate, the quartz plate is heated at 60 ℃ for volatilizing a solvent, another quartz plate is covered, and tweezers are used for moving the quartz plate to discharge bubbles and the color of the quartz plate is uniform. And irradiating with 365nm ultraviolet lamp for 10 s to perform photopolymerization to obtain cured film.
Examples ten
The embodiment of the invention provides a method for preparing a fluorescent liquid crystal material 10, which comprises the following steps:
liquid crystal molecules 5
Chiral dopant 2
Fluorescent molecule 3
Photoinitiator 3
Specific steps for preparing the fluorescent liquid crystal material 10:
(1) The preparation method of fluorescent molecule 3 comprises the following steps:
into a 250mL round bottom flask was charged 3, 7-dibromo-10- (4-methoxyphenyl) -10H-phenothiazine (2.30 g,5 mmol), pinacol biborate (3.80 g,15 mmol), bis (triphenylphosphine) palladium dichloride (0.23 g,0.33 mmol), potassium acetate (1.46 g,15 mmol), and 1, 4-dioxane (90 mL) was added and reacted at 100℃for 15 hours. After the reaction is finished, cooling to room temperature, adding diatomite, filtering to obtain a filtrate, adding an aqueous solution for washing, extracting with dichloromethane, adding anhydrous sodium sulfate into an organic layer for water removal, carrying out suction filtration and rotary evaporation to obtain a yellow solid, adding ethyl acetate for washing, and carrying out suction filtration to obtain a pale yellow solid. The resulting pale yellow solid (2.0 g,4 mmol), triphenylbromoethylene (3.96 g,11.8 mmol), potassium carbonate (2.5 g,18 mmol), tetrakis (triphenylphosphine) palladium (0.27 g,0.22 mmol) were added to a 100mL three-necked flask, nitrogen was purged, and 45mL toluene and 30mL water were added. And heating and refluxing at 110 ℃ for 15 hours. After the reaction is finished, cooling to room temperature, adding an aqueous solution for washing, extracting with dichloromethane, adding anhydrous sodium sulfate into an organic layer for water removal, carrying out suction filtration and rotary evaporation to obtain oily liquid, adding a small amount of dichloromethane for dissolution, and carrying out column chromatography separation to obtain a target product fluorescent molecule 2. The yield of the reaction product was 65%.
The fluorescent molecule 3 base is characterized as follows:
1 H NMR(300MHz,DMSO-d 6 ,TMS)δ H :2.32(s,3H),6.83(d,J＝8.1Hz,2H)，6.68-6.78(m,4H)，6.95-7.38(m,32H)，7.80(d,J＝8.5Hz,2H)ppm.
(2) Liquid crystal molecules 5 (179.55 mg), chiral dopants 1 (12.35 mg) and fluorescent molecules 3 (4 mg) are weighed, a glass bottle is filled with the photoinitiator 3 (12 mg), dichloromethane is added for dissolution, ultrasonic waves are added for ensuring uniform mixing, then liquid crystal mixture is sucked on a quartz plate, the quartz plate is heated at 60 ℃ for volatilizing the solvent, another quartz plate is covered, and tweezers are used for moving the quartz plate to discharge bubbles and the color of the quartz plate is uniform. And irradiating with 365nm ultraviolet lamp for 10 s to perform photopolymerization to obtain cured film.
Test case
Performance testing of the Material obtained in example I
Fluorescent molecule 1 is a phenothiazine derivative with AIE effect, which is tested in pure DMF solution and DMF-H with different water contents respectively 2 Fluorescence intensity in O mixed solvent system. It was found to be non-fluorescent in pure DMF solution when the poor solvent H was added 2 At the O ratio, fluorescence was enhanced, showing a pronounced aggregation-induced emission (AIE) property (as shown in fig. 1).
In the liquid crystal mixed system, different mass percentages of chiral dopants are controlled, and a series of polymer liquid crystal films with structural colors are obtained by utilizing ultraviolet lamp irradiation to generate photo-crosslinking reaction. As fluorescent molecules 1 are added into the high-molecular liquid crystal film, the liquid crystal film emits blue fluorescence under the irradiation of an ultraviolet lamp (as shown in figure 2). The series of liquid crystal films are respectively placed in a JASCO-300 circular polarization luminescence spectrometer for testing, obvious CPL signals are observed, and the liquid crystal polymer films all have Circular Polarization Luminescence (CPL) performance (shown in figure 3); and when chiral dopingWhen the mass percentage of the agent is 5.68%, the luminous asymmetry factor g at the maximum emission wavelength lum Up to 0.71.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A fluorescent compound characterized by the following molecular formula:
wherein R is selected from cyano, methyl, ethyl, propyl, methoxy or carboxyl.
2. The method for producing a fluorescent compound according to claim 1, comprising the steps of:
(1) Will beAdding a reaction solvent into the bisboronic acid pinacol ester, a catalyst and an alkaline agent to perform heating reaction, and performing solid-liquid separation on the reaction liquid to obtain a solid substance; wherein R is selected from cyano, methyl, ethyl, propyl, methoxy or carboxyl;
(2) Mixing the solid substance obtained in the step (1) with triphenylbromoethylene, an alkaline agent and a coupling catalyst, and performing heating reaction in a reaction solvent to obtain the fluorescent compound.
3. Use of a fluorescent compound according to claim 1 for the preparation of a fluorescent chiral liquid crystal film.
4. A fluorescent chiral liquid crystal film prepared from the fluorescent compound of claim 1.
5. The method for preparing a fluorescent chiral liquid crystal film of claim 4, comprising the steps of:
(1) Mixing and dissolving liquid crystal molecules, chiral dopants, fluorescent compounds and photoinitiators in a solvent to obtain a liquid crystal mixture;
(2) Uniformly coating the liquid crystal mixture obtained in the step (1) between two substrates to form a sandwich structure, heating to remove the solvent, performing photopolymerization under ultraviolet irradiation, and removing the substrates to obtain a cured film, namely the fluorescent chiral liquid crystal film.
6. The method of claim 5, wherein in step (1), the liquid crystal molecules are selected from one or more of the following compounds:
7. the method of claim 5, wherein in step (1), the chiral dopant is selected from the group consisting ofWherein n is any integer from 0 to 12, M represents a chiral moiety selected from isosorbide, binaphthyl, cholesterol, menthol or 2- (4, n-propyl) cyclohexyl; r is R 1 Selected from hydrogen, halogen, methyl, ethyl, acetyl.
8. The method of claim 5, wherein in step (1), the photoinitiator is selected from one or more of the following compounds:
9. the method according to claim 5, wherein in the step (1), the mass ratio of the liquid crystal molecules, chiral dopant, fluorescent compound and photoinitiator is 170-180:8-13:2-4:8-12.
10. The method of claim 5, wherein in step (2), the substrate is selected from quartz plate and/or polyester film; wherein the polyester film monomer material is selected from one or more of polyethylene terephthalate, polyurethane, polymethyl methacrylate and polytrimethylene terephthalate.
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| CN113249116A (en) * | 2021-05-20 | 2021-08-13 | 苏州大学 | Fluorescent organic-inorganic silicon oxide liquid crystal material and preparation method thereof |
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